Browsing by Subject "C4"

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Differential sensing of hydrophobic analytes with serum albumins
(2012-05) Ivy, Michelle Adams; Anslyn, Eric V., 1960-
In the last decade, there has been a growing interest in the use of differential sensing for molecular recognition. Inspired by the mammalian olfactory system, differential sensing employs an array of non-selective receptors, which through cross-reactive interactions, create a distinct pattern for each analyte tested. The unique fingerprints obtained for each analyte with differential sensing are studied with statistical analysis techniques, such as principal component analysis and linear discriminant analysis. It was postulated that serum albumin proteins would be applicable to differential sensing schemes due to significant differences in sequence identity between different serum albumin species, and due to the wide range of hydrophobic molecules which are known to bind to these proteins. Consequently, cross-reactive serum albumin arrays were developed, utilizing hydrophobic fluorescent indicators to detect hydrophobic molecules. As such, serum albumin cross-reactive arrays were employed to discriminate subtly different hydrophobic analytes, and mixtures of these analytes, in the form of terpenes and perfumes, plasticizers and plastic explosive mixtures, and glycerides and adipocyte extracts. In this doctoral work, a detailed review of the field of differential sensing, and a thorough study of principal component analysis and linear discriminant analysis in various differential sensing scenarios, are given. These introductory chapters aid in better understanding the methods and techniques applied in later experimental chapters. In chapter 3, serum albumins, a PRODAN indicator, and an additive are shown to discriminate five terpene analytes and terpene doped perfumes. Chapter 4 describes an array with serum albumins, two dansyl fluorophores, and an additive which successfully differentiate the plasticizers found within the plastic explosives C4 and Semtex and simulated C4 and Semtex mixtures. Discrimination of these simulated mixtures was also achieved with this array in the presence of soil contaminants, demonstrating the potential real-world applicability of this sensing ensemble. Finally, chapter 5 details an array consisting of serum albumins, several fluorescent indicators, and a Grubb's olefin metathesis reaction, to differentiate saturated and unsaturated triglycerides, diglycerides, and monoglycerides. Mixtures of glycerides in adipocyte extracts taken from rats with different health states were then successfully discriminated, showing promise for clinical applications in differentiating adipoctyes from pre-diabetic, type 2 diabetic, and non-diabetic individuals.
The use of δ]¹³C values of leporid teeth as indicators of past vegetation
(2013-05) Wicks, Travis Zhi-Rong; Shanahan, Timothy M.; Bell, Christopher J., 1966-
Records of change of [delta]13C values in vertebrate teeth offer an opportunity to gain insight into changes in past vegetation. Increasingly, teeth from small mammals are used for such purposes, but because their teeth grow very rapidly, seasonal changes in vegetation potentially provide a large source of variability in carbon isotope composition, complicating interpretations of small mammal tooth isotope data. To investigate the controls of seasonality on the stable isotope composition of fossil teeth, we constructed a Monte-Carlo-based model to simulate the effects of changes in the seasonal pattern of diet in leporid lagomorphs (rabbits and hares) on the distribution of [delta]¹³C values in random populations of leporid teeth from the Edwards Plateau in central Texas. Changes in mean-state, seasonal vegetation range, and relative season length manifest themselves in predictable ways in the median, standard deviation, and skewness of simulated tooth [delta]¹³C populations, provided sufficient numbers of teeth are analyzed. This Monte Carlo model was applied to the interpretation of a 20,000 year record of leporid tooth [delta]¹³C values from Hall's Cave on the Edwards Plateau in central Texas. Variations in the [delta]¹³C values of teeth deposited at the same time (standard deviation = 1.69%) are larger than changes in the mean vegetation composition reconstructed from bulk organic carbon [delta]¹³C, indicating the influence of short-term variability, making it difficult to assess changes in mean C3/C4 vegetation from the tooth [delta]¹³C data. However, populations of teeth from different climate intervals (e.g., the late Glacial, Younger Dryas, and the Holocene) display changes in the shape of the tooth [delta]¹³C distributions. Interpretation of these changes as shifts in seasonal vegetation patterns that are based upon results from our model are consistent with hypothesized climatic changes. An increase in the standard deviation of the tooth population between the late Glacial and the Younger Dryas -- Holocene is consistent with an increase in seasonality. Furthermore, a shift to more C3-dominated vegetation in the tooth [delta]¹³C distribution during the Younger Dryas is accompanied by a more skewed population -- indicative of not only wetter conditions but an increase in the duration in the C3 growing season. However, late Holocene changes in vegetation are not clear in the tooth data, despite the evidence from bulk organic carbon [delta]¹³C values for an increase in % C3 vegetation of 57%. Small mammal teeth can potentially provide unique insights into climate and vegetation on seasonal and longer timescales that complement other data, but should be interpreted with a careful consideration of local conditions, taxon ecology and physiology, and the dominant timescales of isotope variability.